Process of metal coating metal articles



.May 18, 1948. l c.. 'nluNflfcJN Y 2,441,776

PRocEs-s oF METAL CATINGMETAL ART1cLEs'- originen Fi1ed om.A 21., 1958 2 sneeisL-sheei 1 Ma .y 18, 1948. u. c. TAlNToN 2,441,776

PROCESS 0F METAL CoATlNG METAL ARTICLES Original Filed Oct. 21, 1938 2 Sheets-Sheet 2 k-.INVENTOR U M- /Ma Patented May 18, 1948 PROCESS on METAL coATrNG METAL ARTICLES Urlyu Cliftonv Tainton, Baltimore, Md.; Rolfe Pottberg, administrator of U. C. Tainton, deceased, assignor to Freeport Sulphur Company, New York, N.y Y., a corporation of Delaware- Original application-October. 21;,` 1938', Serial' No.

236,340. Divided'and this application February 15,A 1943;. SeralNo. 475,865

a claims. (ci. 11i-5.2).Y

My invention: relatesrtothe treatment: ofmetal,

particularlyfor thev cleaning of the surface'therezof. The invention is especially eiiectiive for removing rust, scale, carbon andi slag from'the surface of ironand-r steel; and isl'particularly applicable as. a vpreliminaryl treatment to various coatingv operations, such asgalvani-zi-ng, enameling', painting, electroplating or the like` The invention, however, as'will later more fully appear, is' notlimitedV tothe treatn'ientl of ferrous metal. i f

My invention comprisesvthe-stepioi subjecting the'surfaces of metals tothe reducing` action of afmetalmore electropositive than v*the metal being treated, that is having a position the electrochemical scale above that of the metal being treated. For example,l when iron or steellis being treated it may be subjected tothe action of sodium or calcium, which metals are considerably more electropositivethan iron. Morev specifically, my invention comprises the subjection of the `metala articlev to-be treated to the action of'a; more-electropositive'- metal by a method in Whichthearticle is used asA a cathode in a bath comprising compounds of the more electropositive metals, under such conditions that the more electropo'sitivemetal is liberatedat the surface-ofthe article. Y

Inr presenting this invention, a specific em@- bodimentthereofwill-flrst be described, followed byillustrativey modifications and an outline ofthe general principles upon which-it rests.

Accordingly I shall rst describe the cleaning of steel cr ironY wire as a stepin the manufacture of electroplated-zinc coated wire.

Referring to the drawings:

Fig. 1 isa diagrammaticV elevation, mereor less inV section', of'a system forv cleaning andselectroplating the wire;

Fig; 2 Yis a plan viewof the system showny in Fig. 1; and F l Fig. 3 is a diagrammatic longitudinalV elevation of a system for cleaning Wire and then galvanizingit` by a hot'dip operation.

Referring first to` Figs. 1' and 2, the wire II is fed continuously from reel I2successively through cleaning tank I3; wash tank I4, anodic cleaning tank I5; and electroplating tank I6,`to reel I'I. Electrodes I8, I9 and tldepend; into tanks I3,A I5 and IELwhich also contain electrodesV ZI, 22 and respectively. The wire runs over guide rolls 24 mounted`A on theV tanks, and over guide rolls 25 mounted at'the ends of electrodes I8, I9 and 2i); VThe electrodes of'the several tanks are connected to electric current sources 26, 21 and 28, respectively,` electrodes I8, I9 and 20 being respectively negative, positive, andv negative, while electrodes 2l, 22l and 2-3 are-respectively positive, negative, and positive'.` Guide rolls 25 serve to conduct current to wire l I, the-Wire thus: being 2 renderedcathod-icin-tank I3, anodic in tank I5 andagain cathodic in tank I-B. Gas burners 29 are provided for maintaining tank lvin a heated condition.

Tank t3t containsa fused bath of sodium hydroxide through which the wire passes. Current is--passed through the fused bath to electrclyze it, the wire serving as the cathode. In this specifio example of myy invention, the wire passes through the bath at such a rate Ythat each portion thereof remains immersed in the fused bath fora period of about thirty seconds and the current density employed is between and 200 amperes perv square foot of cathodic surface.y

From tankY I3' the wire passes through wash water in tank I4 to remove the adherent sodium hydroxide,.thenceA passing through an aqueous solution of'sulphuric acid in tank E5, the concentration of: this being 20% HzSOi. Here the wire acts as the anode, the current density employed being of 'the order of 100- amperes per square foot or greater.

The wire next passes through an aqueous solution ofzincsulphate and'sulphurieacidin tank I6-, the zinc sulphate being in such an Vamount as togive azinc content of 7 grams per 100 cubic centimetersl of solution and thesulphuric acid about 20%.r .Here the wire; actsl as the cathode, the current density being `of the order of 200 amperes or` greater per square foot of cathodic surface. Here the wire is electropla-ted with zinc. For the anodic treatment in tank-l5, the same composition maybe employed as that in thelcoating cfV plating tank I6;

The treatment in tank I3 is the most significant stage of the process so far as this particular patent application is concerned. This treatment effectively cleans the surface of the wire, fully removing those obstacles to effective coating of ferrous metal. Moreover, this treatment produces a passive condition of the surface of the metal. This passivity of the metalsuriace gives it a considerable degree of resistance to corrosive influences.

.Current densities in 'this sodium hydroxide- Acathodic cleaningv operation may Vary over substantial ranges. However, suicient current density `and a sufficient period of time of the metal in the cleaning bath should ordinarilyy be, employed to' effect a substantially complete reduction of surface oxides While the metal is in-ly the bath. Ordinarily the current density should be between 25 and 300 amperesrper square foot of cathode surface. Most commonly the current is from 100 to 200 amperes per square foot of cathode surface.

For the most effective results, the electrolysis of the fused sodium hydroxide should beso 'carried outV that the elemental sodiumfliberated does not collect in sensible amounts, preferablynot To eiect this result I employ conditions during electrolysis such thatthe sodium vas fast as it is separated from the sodium hydroxide,"

in the elemental state, is dissolved by or diifused.v`

into the bath of sodium hydroxide, andlconse-` quently does not gather or collect upon the surface of the article acting as cathode.

Under such conditions the sodium acts intwo ways upon the oxides and other compounds onr the articles surface: iirstly, the sodium acts re-V ducingly at the instant of its liberation from,

the sodium hydroxide, that is, it acts in its nascent condition; and secondly, the article is bathed by a solution of sodium in sodium hydroxide which acts reducingly upon any compounds on the artieles surface.

'I'he most easily imposed conditions for effecting the treatment with sodium without collecting sensible quantities of sodium on the surface of the article being treated is by the control of the temperature of the fused bath of sodium hydroxide. I maintain this fused bath at a temperature above thatat which sodium collects upon the cathode, By keeping the bath at temperatures more than 20 C. in excess of the melting point of sodium'hydroxide, the sodium is prevented from collecting on the cathode. At'such temperatures the liberated sodium, which does not act immediately upon the compounds on the cathode surface, dissolves forthwith in the sodium hydroxide and thus the article being treated issurrounded Vwith a highly reducing liquid which is exceedingly elective in rapidly reducing the compounds which may be upon the surface.

Preferably I employ the sodium hydroxide bath at a minimum temperature of 350 C. but, as im# plied above, I may go as low as a temperature just in excess of 20 abovethe melting point of the sodium hydroxide. Consequently I may use a temperature as low as just in excess of'338" C. in the case of pure sodium hydroxide. Since or less impure, their melting points are lower than that of the pure hydroxide, ordinarily ranging from about 295 C. to 300 C., consequently with these impure sodium hydroxides VI may operate at somewhat lower temperatures, if desirable, namely at temperatures which are J'ust in excess of 315 to 320 C.

High chromium steels, including the so-called stainless steels such as the well known"188 Y(18% chromium, and 8% nickel), are advantageously treated by my cleaning process. In treating these high chromium steels it is usually well to employ temperatures of the order of 538 C.

If, in the operation of the process given above as an example of my invention, the bath of sodium hydroxide is maintained at-a temperature substantially above 550 C. the surface of the iron or steel becomes oxidized when it passes from the fused sodium hydroxide in tank I3 into the air. This condition can frequently be obviated by maintaining the fused bath of sodium hydroxide at a temperature below 550 C., at 500 C., for example. By using the cleaning bath' at this temperature the oxidation of the treated metal is usually avoided by preventing at the outset the condition of the steel surface which leads to oxidation.

In carrying out the process above described, it may be useful in some cases to employ tempounds. most commercial sodium hydroxides are more peratures of the-fused bath in excess of 550 C. It may be desired, for example, to eect an annealing of wire in the fused bath at a temperature say of- 600 C.- If such a temperature of the fusedbath is employed in tank I3 the surface ,of the wire .will Voxidize when it enters the air.

The oxides von the surface, thus produced, however, are vnot so closely adherent as those which normally occur.. on ferrous surfaces and they may easily be removed by a relatively mild pick- Yling operation in` an aqueous acidrbath, such a pickling operation being much more easily and inexpensively carried out than if the metal had not previously been subjected to the fused bath treatment. Of course,'when the article, after its treatment in the sodium hydroxide bath,`lis given a treatment such' .as the anodic treatment illustrated in Figs. 1 and 2, the oxides are effectively removed.

Steam directedalong the surface of the wire as it issues from theA bath seems to have an action in addition to that which it directly effects upon the `wire as it issues from the fused bath, for instance, in blowing off considerable of the sodium hydroxide. It appears to modify 'somewhat the character of the bath with which it contacts in that it adds a small amount of H2O to the bath which combines with the oxidizing materials therein and thereby renders the exit portion of the bathrelatively free from the tendency to furnish actively oxidizing materials to the wire or other metal article.

Other means for preventing the rapid oxldaf tion of the metal as it leaves the fused cleaning bath may be employed. VThe oxygen in the air appears to be a factor in the reoxidation of the metal as it leaves the fused bath. By providing an atmosphere of a non-oxidizing gas, particularly one having a` reducing action,i reoxidation is substantially or entirely prevented.

My process is not limited in its application to sodium hydroxide. .Other compounds of sodium may be used, or mixtures of different com- Nor is my process limited to the use of compounds of sodium. Compounds of the other alkali metals may lbe used, those of potassium being particularly suitable. I- may also use compounds of the alkaline earth metal group including magnesium, those of calcium being economically advantageous. I-Iereafter, when referring generically to these various metals and their compounds, I shall usually designate them as highly electropositive metals or compounds thereof.

Not only with sodium hydroxide but with other compounds of sodium as Well as compounds of the other metals of the alkali metal group the metals of the alkaline earth group, I prefer to operate at temperatures substantially above their melting points. I find that the reducing action of these -highly electropositive metals is much more effective if the operating temperature of the bath lis substantially in excess of the melting point of the compound or mixture of compounds which is used. Ordinarily the operating temperature of the bath should be in excess of twenty degrees above the melting point of the bath. By Y so proceeding, I find that I avoid the superficial reduction of compounds-which may occur if lower `temperatures are used, moreover the resulting reduced metal is much more easily detached than if the lower temperatures were to be used.

-Variety of effects may be produced, thus enabling droxide.

one to select the conditions most` suitable. for his particular materialand problem. For example, if lower temperatures offoperation, than those securable bythe usev of .sodium hydroxide, arer desired, such temperatures' caribe. obtained by. the use. of compounds' of lower: meltingpoints, such, for example', as sodium'v nitrite; (fusingf at 213 C.) eithera-lone or mixedwith sodium*A hy- Byl the judicious mixing; of various lsodium and potassium salts, asis well. known, a. rather wide range' ofA fusion points' may be secured. I

VIn Fig. 3- L have illustrated` diagrammatically an equipment for eifectingfmyI method ofr cleaning wire in conjunction with' a hot dipl galvanizing. A tankA @tris adapted" to containfmolten lead in its bottom portion. This tank' is provided With a partition 6l' which extends. completely across the tanlifbut terminates short of the bottom, its lower end' extending: Well. into the lead bath. The lefthandcompartment contains a molten bath of ai mixture of.v sodium and potassium chloride and' ther-ight hand. compartment contains molten zinc', both baths resting, obviously, on. the bath of leadxin' the bottom of the tank; Wire Il is-fedcontinuously'a'round rollers 62 first through the fused. bath of sodium and potassium chloride, therr through the'y lead in the bottom of the tan'k,..and.then through'the galvanizing bathofv zinc. A suitable mixture may consist of sixty partsoflsodiumchloride and forty parts of potassium chloride. Instead of the chlorides of thesey alkali metals, fluorides may be satisfactorily employed.

Arranged adjacent to the Wire in themolten chloride are anodesA 63; these anodesv extending along the length of the wire. The wireis used as aV cathode as inthe preceding examples of my process. As will be readily apparent this mode of treatment avoids the chemical` interaction of the Zinc and the constituents of the fused bath and yet permits ofthe Wire being taken into the coating medium-Withoutlfirst lpassing into the air. Consequently even though the fused bath be operatedI at a4 temperature above 550 C., oxidation cf the Wire is largely' or completely obviated. This processthus furnishes a further mode of avoidance of the tendency of the metal toY be oxidized.

Usually in carrying out my cleaning operation it is important to maintainA the fused bath relatively constant in composition or at least to allow variations only Within denite limits. If there is undue variation in the composition of the fused bath the temperature will vary, unduly. If, for example, sodium hydroxide is` used for the bath undue formation of sodium carbonate through absorption fromtheair of carbon dioxide will lead to such' an elevation of the' melting point ofy the bathr as to give bath temperatures too high for the most satisfactory operationv of my process. Where,v for instance, it is desired to operate the bath of sodium hydroxide at a temperature below" 550 C; to'prevent the'ready oxidability of the metal, it is necessary that meansV be provided toV prevent the absorption of such an amount of carbon dioxide as' Wiil raise the melting point above the desiredoperating temperature. lThe carbonatecontent of the fused bath will of course depend upon the rate of removal of the mixture of sodium hydroxide and sodium carbonate upon the surface ofthe metal being treated, the rate of. replenishment of the fused bath by theaddition of' pure sodium hydroxide, and the rate of" absorption ofl carbon dioxide. The most eiiective way of keeping the electrolytically or otherwise.

carbon dioxide absorption at the necessary minimum is by providing a cover for the fused bath cleaning tank.

The loss of sodium hydroxide, or other bath constituent, fromthe fused bath, due to its being carried away on the surface of the article treated, may be minimized in various Ways as by wiping the wire or other article as it issued from the bath.

I have already indicated, in my description of the use of a fused bath of sodium hydroxide, that I prefer to operate the bath under such conditions that I obtain the conjoint action of sodium in thenascent' state and sodium dissolved in the sodium hydroxide. The solution ofthe reducing metal is a highly important feature of my invention. A consequence of its presence is that reduction of oxides and other compounds is not limited tothose portions of the articles surface which are acting efficiently as cathode. For example, the oxides en both sides of an article are reduced even when but oneside of such article acts as cathode. The importance of this a-ction of the solution of highly electropositive metal is obvious. Many articlesV to be cleaned are of such shape that it is practically impossible for all parts of their surface to act efiiciently as cathode surfaces, as, for example, articles of a tubular construction', those which are deeply recessed, and the like. As a result ofl the article being surrounded by a solutionof the reducing-metal, all portions of the articles surface can be effectively treated.

I am able to reduce oxides, and other compounds, effectively even when the article being treated does not act as cathode. By producing a: solution of the highly electro-positive metal instead of collecting it upon the cathode, as already pointed out, an article in the fusedV bath maybe subjectedV to the reducing action of the solution even though such article is in no Way electrically connected with the cathode.

Accordingly, my invention, in its broader aspect, includes the idea of subjecting metalarticles to a solution of highly electro-positive metal in a fused bath; For example, articles having highly oxidized surfaces may be effectively cleanedv by immersing them for a substantial time in a solution of. sodiumrin fused sodium hydroxide, regardless of hoW the solution is prepared, Whether The solution obviously may be prepared in various Ways. Elemental sodium may be graduallyy added to a fused bath'of sodium hydroxide in any manner desired. Probably the most effective Way to maintain a solution of sodium in the hydroxide is by introducing it in the manner already pointed out, namely by electrolyzing a solution of sodium hydroxide at a suiiiciently elevated temperature to cause the liberated sodium to diffuse into the fused bath.

My process is not limited to the treatment. of ferrous metals. Articles of various metals may be efficiently cleaned by subjecting them to the action ofmetals having a greater aflinity for oxygen' than the metal being treated.

For example, I have effectively cleaned articles of copper, bronze, and nickel-chromiumalloys by using them as cathodes in the electrolysis of a fused bath of sodium hydroxide. It will be readily appreciated that the essential principles of this invention may be. applied to metals generally, varying, as desired and as special conditions demand, the details of the operation.

Various modifications in my process areY feasible. For example, it is practicable to produce alloy surfaces on an article at the same time it is treated to reduce oxides and other reducible compounds.

the copper as cathode to electrolysis in a fused bath of sodium hydroxide in which Zinc oxide is dissolved, the copper not only being cleaned but the zinc being deposited to alloy with the surface of the copper. Similarly, the copper may be provided with a surface of a copper-tin alloy by subjecting the copper as cathode to electrolysis in a fused bath of sodium hydroxide in which tin oxide has been dissolved. Lead may be deposited upon ferrous surfaces if a lead compound is present in the fused bath.

A further means of reducing or overcoming the tendency to reoxidation is to reduce the current density just before the article leaves the bath. For example, if wire is being treated in a caustic soda bathand acurrent density of 100 amperes per square foot of cathode surface is being employed to clean the surface, the current density kmay be reduced to 10 amperes or less per square foot of cathode surface just before the wire leaves the fused bath.

The treatment of the article either electrolytically or without current accomplishes the deoxidation of the oxides, scale and the like within the bath, and it is understood that the treatment without current may be preceded by and followed by the electrolytic and oxide-preventing treatments, as described in connection with the electrolytic deoxidation and that the treated material may be Vbrought out through subsequent fused baths as illustrated, for instance, in Fig. 3 with a corresponding coating of the surface of the article.

This application is a division of my co-pending application Serial No. 236,340, led October 21, 1938, now Patent No. 2,311,139, which application is in part a continuation of application Serial No. 630,233, led August 24, 1932,'app1ication Serial No. 692,378, filed October 6, 1933, and application Serial No. 128,682, filed March 2, 1937, now Patent ANo. 2,134,457, dated October 25, 1938.

I claim:

1. In a process for treating a metal article to remove oxides, scale an-d the like, the steps of providing a bath of a molten compound of a metal from the group consisting f the alkali and alkali earth metals and containing in solution a metal also from said group and electropositive relative to the treated metal of the article, introducing said article into said bath, maintaining said bath at a temperature below the boiling point of said treating metal and suciently high above the fusion point of the molten compound to maintain said supplied metal in solution in said bath at the area of contact with said article whereby to avoid a deposit of said treatingmetal on said article, continuing said treatment for a sufficient length of time with suiiicient treating metal in solution to complete reduction of the oxides, scale and the like in the bath without accumulation of a deposit of said treating metal on the article, passing said treated metal article free of deposit of said treating metal into a contiguous bath of an inert, relatively non-coating metal, and then passing said treated metal article into a contiguous bath of a molten coating metal substantially free of said alkali metal and accumulating said coating metal in direct contact with the surface of the article.

2. The process of treating a metal article to For instance, it is possible to give copper a zinc-copper alloy surface by subjecting remove oxides, scale and the like comprising the steps of placing said article in circuit directly connected to an electro-negative source and subjecting it to electrolysis as a cathode in a molten bath of a compound of a metal of the group consisting of alkali and alkali earth metals adapted to 'be liberated at the surface of the cathode in said electrolysis, and subjecting the article to the action of said molten bath of the compound ata temperature below the boiling point of the liberated metal and sufficiently in excess ofY the fusion point of the molten compound to dissolve the liberated metal in said bath and avoid a deposit of said metal on said article, maintaining said treatment for a'suiiicient time to completely reduce oxides, scale and the like While the article is in the bath and then delivering'said treated article from said molten bath free of any sensible deposit of said dissolved metal through a contiguous bath of a molten, inert, relatively noncoating metal to a contiguous bath of a molten coating metal substantially free of said liberated metal and accumulating as a deposit in direct contact with the surface of said article.

3. In a process for treating a metal article to remove oxides, scale and the like, the steps of providing a bath of a molten compound of a metal from the group consisting of sodium, calcium, potassium and magnesium and containing in solution metallic sodium, introducing said article into said bath, maintaining said bath at a temperature between 315 C. and 600 C. and sufliciently in excess of the diffusion point of the molten compound to dissolve the sodium in said bath and avoid a deposit of sodium on said article, continuing said treatment for a suiicient length of time With sufficient sodium metal in solution to complete the reduction of the oxides, scale and the like in the bath Without accumulation of said sodium metal on the article, passing said treated metal article free of sodium into a contiguous bath of molten lead and then passing said treated metal article into a contiguous molten bath of molten zinc substantially free of sodium and accumulating as a deposit in direct Contact with the surface of said article.

URLYN CLIFTON TAINTON.

REFERENCES CITED The following references are of record in the file of this patent:

STATES PATENTS Number Name Date 781,230 Rodman Jan. 31, 1905 800,984 Chance Oct. 3, 1905 1,114,635 Nelson Oct. 20, 1914 1,276,977 Shoemaker Aug. 27, 1918 1,330,399 Shoemaker Feb, 10, 1920 1,378,052 Peacock May 17, 1921 1,545,305 Calpo et a1. July 7, 1925 1,741,388 Wehr et a1 Dec. 31, 1929 1,942,121 Patterl Jan. 2, 1934 2,134,457 Tainton Oct. 25, 1938 2,172,933 Daesen et a1 Sept. 12, 1939 2,261,744 Ostrofsky Nov 4, 1941 2,311,099 VTainton Feb. 16, 1943 2,311,139 Tainton Feb. 16, 1943 FOREIGN PATENTS Number Country Date 203 Great Britain 1857 386 Great Britain 1857 257,262 Great Britain 1927 

